U.S. patent number 6,630,465 [Application Number 10/059,668] was granted by the patent office on 2003-10-07 for synergistic insecticidal compositions.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Raymond Frank Borysewicz, Paul E. Rensner, Michael Frank Treacy.
United States Patent |
6,630,465 |
Treacy , et al. |
October 7, 2003 |
Synergistic insecticidal compositions
Abstract
The present invention provides a synergistic insecticidal
composition comprising as essential active ingredients a neuronal
sodium channel antagonist and an arylpyrrole insecticide. Also
provided are methods for synergistic insect control and crop
protection.
Inventors: |
Treacy; Michael Frank (Newtown,
PA), Borysewicz; Raymond Frank (Hamilton Square, NJ),
Rensner; Paul E. (Yardley, PA) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DE)
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Family
ID: |
26822327 |
Appl.
No.: |
10/059,668 |
Filed: |
January 29, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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521988 |
Mar 9, 2000 |
6342518 |
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Current U.S.
Class: |
514/228.8;
424/405; 514/229.8; 514/229.2; 514/229.5 |
Current CPC
Class: |
A01N
43/36 (20130101); A61P 7/04 (20180101); A01N
43/36 (20130101); A01N 47/38 (20130101); A01N
47/34 (20130101); A01N 43/56 (20130101); A01N
37/50 (20130101); A01N 43/36 (20130101); A01N
2300/00 (20130101) |
Current International
Class: |
A01N
43/36 (20060101); A01N 43/34 (20060101); A01N
051/00 (); A01N 043/56 (); A01N 047/40 () |
Field of
Search: |
;514/228.8,229.2,229.5,229.8 ;424/405 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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WO 96/10560 |
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Nov 1996 |
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WO |
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97/40692 |
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Nov 1997 |
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WO |
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WO 98/23153 |
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Apr 1998 |
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WO |
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WO 98/23154 |
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Jun 1998 |
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WO |
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WO 98/25461 |
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Jun 1998 |
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WO |
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Other References
Senn, Robert et al. (DN 128:11112, HCAPLUS, abstract of WO
97/40692).* .
Gregory T. Payne, et al., Structure-Activity Relationships for the
Action of Dihydropyrazole Insecticides on Mouse Brain Sodium
Channels, Pesticide Biochemistry and Physiology, Aug. 1, 1998, vol.
60, No. 3. .
Keith D. Wing, et al., A Novel Oxadiazine Insecticide Is
Bioactivated in Lepidopteran Larvae, Archives of Insect
Biochemistry and Physiology 37:91-103 (1998)..
|
Primary Examiner: Qazi; Sabiha
Attorney, Agent or Firm: Keil & Weinkauf
Parent Case Text
This application is a division of Ser. No. 09/521,988 filed Mar. 9,
2000 now U.S. Pat. No. 6,342,518, which claims benefit of No.
60/124,228 filed Mar. 12, 1999, and claims benefit of No.
60/158,202 filed Oct. 7, 1999
Claims
What is claimed is:
1. A synergistic insecticidal composition comprising as active
components (a) a neuronal sodium channel antagonist of formula III
##STR9## wherein W is O or S; Z' is, in each case, independently
selected from the group consisting of H; halogen; OH; CN; NO.sub.2
; C.sub.1 -C.sub.6 alkyl optionally substituted with one or more
halogen, C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 haloalkoxy,
C.sub.3 -C.sub.6 cycloalkyl, C.sub.2 -C.sub.6 alkenyloxy or
sulfonyloxy groups; C.sub.1 -C.sub.6 alkoxy optionally substituted
with one or more halogen, C.sub.1 -C.sub.3 alkoxy or C.sub.3
-C.sub.6 cycloalkyl groups; C.sub.1 -C.sub.6 alkoxycarbonyl,
C.sub.3 -C.sub.6 cycloalkylcarbonyloxy, phenyl optionally
substituted with one or more halogen, C.sub.1 -C.sub.4 alkyl, or
C.sub.1 -C.sub.4 alkoxy groups; and aminocarbonyloxy optionally
substituted with one or more C.sub.1 -C.sub.3 alkyl groups; t is an
integer of 1, 2, 3 or 4; G is H; C.sub.1 -C.sub.6 alkyl optionally
substituted with one or more halogen, C.sub.1 -C.sub.4 alkoxy,
C.sub.1 -C.sub.6 haloalkoxy, CN, NO.sub.2, S(O).sub.u R.sub.14,
COR.sub.15, CO.sub.2 R.sub.16, phenyl or C.sub.3 -C.sub.6
cycloalkyl groups; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6
haloalkoxy; CN; NO.sub.2 ; S(O).sub.u R.sub.17 ; COR.sub.18 ;
CO.sub.2 R.sub.19 ; phenyl optionally substituted with one or more
halogen, CN, C.sub.1 -C.sub.3 haloalkyl, or C.sub.1 -C.sub.3
haloalkoxy groups; C.sub.3 -C.sub.6 cycloalkyl; or phenylthio; Q is
phenyl optionally substituted with one or more halogen, CN, SCN,
NO.sub.2, S(O).sub.u R.sub.20, C.sub.1 -C.sub.4 alkyl, C.sub.1
-C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxyalkyl, C.sub.1 -C.sub.6
alkoxy, C.sub.1 -C.sub.6 haloalkoxy, or NR.sub.21 R.sub.22 groups;
u is an integer of 0, 1 or 2; R.sub.14, R.sub.15, R.sub.16,
R.sub.18, R.sub.19, R.sub.21 and R.sub.22 are each independently H
or C.sub.1 -C.sub.6 alkyl; R.sub.17 and R.sub.20 are each
independently C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sub.33 is CO.sub.2 R.sub.34 ; R.sub.34 is H, C.sub.1 -C.sub.6
alkyl, C.sub.1 -C.sub.6 haloalkyl, phenyl or halophenyl; and the
dotted line configuration {character pullout} represents a double
bond or a single bond; and (b) an arylpyrrole insecticide of
formula VI ##STR10## Hal is Cl or Br; x is an integer of 1, 2, 3,
4, 5 or 6; D is H, C.sub.1 -C.sub.6 alkyl optionally substituted
with one or more halogen, CN, OH, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, C.sub.1 -C.sub.5 alkylthio, C.sub.1 -C.sub.4
alkylcarbonyloxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.6
alkenylcarbonyloxy, phenylcarbonyloxy, halophenylcarbonyloxy,
phenoxy, halophenoxy, phenyl, halophenyl or C.sub.1 -C.sub.3
alkylphenyl groups, C.sub.2 -C.sub.6 alkenyl, C.sub.2 -C.sub.6
haloalkenyl, CN, C.sub.2 -C.sub.6 alkynyl, C.sub.2 -C.sub.6
haloalkynyl, di-(C.sub.1 -C.sub.4 alkyl) aminocarbonyl or C.sub.3
-C.sub.6 polymethyleneiminocarbonyl; L is H or halogen; M and
M.sup.1 are each independently H, halogen, CN, NO.sub.2, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4
alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkylthio,
C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylsufonyl,
C.sub.1 -C.sub.4 haloalkylsulfonyl, C.sub.1 -C.sub.4 alkylcarbonyl,
C.sub.1 -C.sub.4 haloalkylcarbonyl, NR.sub.35 R.sub.36 or when M
and M.sup.1 are attached to adjacent carbon atoms, they may be
taken together with the carbon atoms to which they are attached to
form a ring in which MM.sup.1 represents
and wherein components (a) and (b) are present in synergistically
effective amounts.
2. The composition according to claim 1 wherein Ar is the radical
##STR12##
3. A method for synergistic insect control which comprises
contacting said insect with a combination of (a) a neuronal sodium
channel antagonist of formula III ##STR13## wherein W is O or S; Z'
is, in each case, independently selected from the group consisting
of H; halogen; OH; CN; NO.sub.2 ; C.sub.1 -C.sub.6 alkyl optionally
substituted with one or more halogen, C.sub.1 -C.sub.3 alkoxy,
C.sub.1 -C.sub.3 haloalkoxy, C.sub.3 -C.sub.6 cycloalkyl, C.sub.2
-C.sub.6 alkenyloxy or sulfonyloxy groups; C.sub.1 -C.sub.6 alkoxy
optionally substituted with one or more halogen, C.sub.1 -C.sub.3
alkoxy or C.sub.3 -C.sub.6 cycloalkyl groups; C.sub.1 -C.sub.6
alkoxycarbonyl, C.sub.3 -C.sub.6 cycloalkylcarbonyloxy, phenyl
optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkyl, or C.sub.1 -C.sub.4 alkoxy groups; and aminocarbonyloxy
optionally substituted with one or more C.sub.1 -C.sub.3 alkyl
groups; t is an integer of 1, 2, 3 or 4; G is H; C.sub.1 -C.sub.6
alkyl optionally substituted with one or more halogen, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.6 haloalkoxy, CN, NO.sub.2,
S(O).sub.u R.sub.14, COR.sub.15, CO.sub.2 R.sub.16, phenyl or
C.sub.3 -C.sub.6 cycloalkyl groups; C.sub.1 -C.sub.6 alkoxy;
C.sub.1 -C.sub.6 haloalkoxy; CN; NO.sub.2 ; S(O).sub.u R.sub.17 ;
COR.sub.18 ; CO.sub.2 R.sub.19 ; phenyl optionally substituted with
one or more halogen, CN, C.sub.1 -C.sub.3 haloalkyl, or C.sub.1
-C.sub.3 haloalkoxy groups; C.sub.3 -C.sub.6 cycloalkyl; or
phenylthio; Q is phenyl optionally substituted with one or more
halogen, CN, SCN, NO.sub.2, S(O).sub.u R.sub.20, C.sub.1 -C.sub.4
alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxyalkyl,
C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 haloalkoxy, or NR.sub.21
R.sub.22 groups; u is an integer of 0, 1 or 2; R.sub.14, R.sub.15,
R.sub.16, R.sub.18, R.sub.19, R.sub.21 and R.sub.22 are each
independently H or C.sub.1 -C.sub.6 alkyl; R.sub.17 and R.sub.20
are each independently C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6
haloalkyl; R.sub.33 is CO.sub.2 R.sub.34 ; R.sub.34 is H, C.sub.1
-C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, phenyl or halophenyl;
and the dotted line configuration {character pullout} represents a
double bond or a single bond; and (b) an arylpyrrole insecticide of
formula VI ##STR14## Hal is Cl or Br; x is an integer of 1, 2, 3,
4, 5 or 6; D is H, C.sub.1 -C.sub.6 alkyl optionally substituted
with one or more halogen, CN, OH, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, C.sub.1 -C.sub.5 alkylthio, C.sub.1 -C.sub.4
alkylcarbonyloxy, C.sub.1 -C.sub.4 haloalkylthio, C.sub.2 -C.sub.6
alkenylcarbonyloxy, phenylcarbonyloxy, halophenylcarbonyloxy,
phenoxy, halophenoxy, phenyl, halophenyl or C.sub.1 -C.sub.3
alkylphenyl groups, C.sub.2 -C.sub.6 alkenyl, C.sub.2 -C.sub.6
haloalkenyl, CN, C.sub.2 -C.sub.6 alkynyl, C.sub.2 -C.sub.6
haloalkynyl, di-(C.sub.1 -C.sub.4 alkyl) aminocarbonyl or C.sub.3
-C.sub.6 polymethyleneiminocarbonyl; L is H or halogen; M and
M.sup.1 are each independently H, halogen, CN, NO.sub.2, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4
alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkylthio,
C.sub.1 -C.sub.4 haloalkylthio, C.sub.1 -C.sub.4 alkylsufonyl,
C.sub.1 -C.sub.4 haloalkylsulfonyl, C.sub.1 -C.sub.4 alkylcarbonyl,
C.sub.1 -C.sub.4 haloalkylcarbonyl, NR.sub.35 R.sub.36 or when M
and M.sup.1 are attached to adjacent carbon atoms, they may be
taken together with the carbon atoms to which they are attached to
form a ring in which MM.sup.1 represents
and wherein components (a) and (b) are applied in synergistically
effective amounts.
4. The method according to claim 3 wherein Ar is the radical
##STR16##
5. The composition according to claim 1 wherein the ratio of the
neuronal sodium channel antagonist to the arylpyrrole insecticide
is about 1:10 to 1:50.
6. The composition according to claim 5 wherein said neuronal
sodium channel antagonist and said arylpyrrole insecticide are
dispersed in an inert solid or liquid diluent.
7. The composition according to claim 1 wherein the dotted line
configuration {character pullout} represents a double bond.
8. The composition according to claim 7 wherein the formula III
compound is in the S-form.
9. The composition according to claim 8 wherein W is O; X is
trifluoromethoxy and is in the 4-position; Y is trifluoromethyl and
is in the 3-position; Z is CN and is in the 4-position; A is
CH.sub.2 ; n is 0; m, p and q are each independently 1; R and
R.sub.1 are each independently H; Z' is Cl; R.sub.33 and G are each
independently CO.sub.2 CH.sub.3 ; and Q is
p-(trifluoromethoxy)phenyl.
10. The composition according to claim 1 wherein D is H or
ethoxymethyl; Ar is phenyl substituted with one or two halogen or
halomethyl groups; and x is 1.
11. The method according to claim 3 wherein the neuronal sodium
channel antagonist is present in a ratio to the arylpyrrole
insecticide of about 1:10 to 1:50.
12. The method according to claim 3 wherein the dotted line
configuration {character pullout} represents a double bond.
13. The method according to claim 12 wherein the formula III
compound is in the S-form.
14. The method according to claim 13 wherein W is O; X is
trifluoromethoxy and is in the 4-position; Y is trifluoromethyl and
is in the 3-position; Z is CN and is in the 4-position; A is
CH.sub.2 ; n is 0; m, p and q are each independently 1; R and
R.sub.1 are each independently H; Z' is Cl; R.sub.33 and G are each
independently CO.sub.2 CH.sub.3 ; and Q is
p-(trifluoromethoxy)phenyl.
15. The method according to claim 3 wherein D is H or ethoxymethyl;
Ar is phenyl substituted with one or two halogen or halomethyl
groups; and x is 1.
16. A method for protecting a plant from infestation and attack by
insects which comprises applying to the foliage or stem of said
plant a synergistically effective amount of a composition according
to claim 1.
17. The method according to claim 16 wherein the plant is
cotton.
18. The method according to claim 16 wherein the insect is
lepidoptera or coleoptera.
Description
BACKGROUND OF THE INVENTION
Although insecticidal agents and compositions have been developed
to control insect pests such as agrohorticultural pests or hygienic
pests, and in practice have been used as a single or a mixed agent,
economically efficient and ecologically safe insect control
compositions are still being sought. Insecticidal compositions
which allow for reduced effective dosage rates, increased
environmental safety and lower the incidence of insect resistance
are highly desirable. The rotational application of insect control
agents having different modes of action may be adopted for good
pest management practice, however, this approach does not
necessarily give satisfactory insect control. Combinations of
insect control agents have been studied, however, a high
synergistic action has not always been found. Obtaining an
insecticidal composition which demonstrates no cross-resistance to
existing insecticidal agents, no toxicity problems and little
negative impact on the environment is extremely difficult.
Therefore, it is an object of this invention to provide a
synergistic insecticidal composition which demonstrates a high
controlling effect with concomittant reduced crop production cost
and reduced environmental load.
It is another object of this invention to provide methods for
synergistic insect control and enhanced crop protection.
SUMMARY OF THE INVENTION
The present invention provides a synergistic insecticidal
composition comprising as essential active ingredients a
synergistically effective amount of a neuronal sodium channel
antagonist and an arylpyrrole insecticide.
The present invention also provides a method for synergistic insect
control which comprises contacting said insect with a
synergistically effective amount of a combination of a neuronal
sodium channel antagonist and an arylpyrrole insecticide.
The present invention further provides a method for the enhanced
protection of plants from infestation and attack by insects.
DETAILED DESCRIPTION OF THE INVENTION
When two or more substances in combination demonstrate unexpectedly
high biological activity, for example, insecticidal activity, the
resulting phenomenon may be referred to as synergism. The mechanism
of synergism is not fully understood, and quite possibly may differ
with different combinations. However, the term synergism, as used
in this application designates a cooperative action encountered in
a combination of two or more biologically active components in
which the combined activity of the two or more components exceeds
the sum of the activity of each component alone.
Surprisingly, it has now been found that a composition which
comprises a combination of a neuronal sodium channel antagonist and
an arylpyrrole insecticide provides superior insect control at
lower levels of the combined active agents than may be achieved
when the neuronal sodium channel antagonist or the arylpyrrole
insecticide is applied alone.
As used in this application, the term neuronal sodium channel
antagonist designates a compound which is capable of preventing the
ability of a neuron cell to transfer sodium ions across the cell
membrane. A neuron cell thus affected is unable to fire, resulting
in paralysis, and ultimately mortality, in the target host.
Descriptions of neuronal sodium channel antagonists and their mode
of action may be found in Pesticide Biochemistry and Physiology,
60: 177-185 or Archives of Insect Biochemistry and Physiology, 37:
91-103, both of which are hereby incorporated by reference.
Neuronal sodium channel antagonists include compounds such as those
described in U.S. Pat. Nos. 5,543,573; 5,708,170; 5,324,837 and
5,462,938, among other publications. Exemplary of the neuronal
sodium channel antagonist compounds useful in the composition of
this invention are those compounds having the structural formula
##STR1## ##STR2##
wherein A is CR.sub.4 R.sub.5 or NR.sub.6 ; W is O or S; X, Y, Z,
X', Y' and Z' are each independently H; halogen; OH; CN; NO.sub.2 ;
C.sub.1 -C.sub.6 alkyl optionally substituted with one or more
halogen, C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 haloalkoxy,
C.sub.3 -C.sub.6 cycloalkyl, C.sub.2 -C.sub.6 alkenyloxy or
sulfonyloxy groups; C.sub.1 -C.sub.6 alkoxy optionally substituted
with one or more halogen, C.sub.1 -C.sub.3 alkoxy or C.sub.3
-C.sub.6 cycloalkyl groups; C.sub.1 -C.sub.6 alkoxycarbonyl,
C.sub.3 -C.sub.6 cycloalkylcarbonyloxy, phenyl optionally
substituted with one or more halogen, C.sub.1 -C.sub.4 alkyl, or
C.sub.1 -C.sub.4 alkoxy groups; aminocarbonyloxy optionally
substituted with one or more C.sub.1 -C.sub.3 alkyl groups; C.sub.1
-C.sub.6 alkoxycarbonyloxy; C.sub.1 -C.sub.6 alkylsulfonyloxy;
C.sub.2 -C.sub.6 alkenyl; or NR.sub.12 R.sub.13 ; m, p and q are
each independently an integer of 1, 2, 3, 4, or 5; n is an integer
of 0, 1 or 2; r is an integer of 1 or 2; t is an integer of 1, 2, 3
or 4; R, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each
independently H or C.sub.1 -C.sub.4 alkyl; R.sub.6 is H, C.sub.1
-C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6
alkoxyalkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.6 haloalkoxy,
C.sub.2 -C.sub.6 alkenyl, C.sub.2 -C.sub.6 alkynyl, C.sub.1
-C.sub.6 alkylcarbonyl, C.sub.1 -C.sub.6 alkoxycarbonyl, C.sub.1
-C.sub.6 alkylthio, or C.sub.1 -C.sub.6 haloalkylthio; R.sub.7 and
R.sub.8 are each independently H; halogen; C.sub.1 -C.sub.6 alkyl;
C.sub.1 -C.sub.6 alkylcarbonyloxy; or phenyl optionally substituted
with one or more halogen, CN, NO.sub.2, C.sub.1 -C.sub.6 alkyl,
C.sub.2 -C.sub.6 haloalkyl, C.sub.1 -C.sub.6 alkoxy or C.sub.1
-C.sub.6 haloalkoxy groups; R.sub.9 and R.sub.10 are each
independently H, or C.sub.1 -C.sub.4 alkyl; R.sub.11 is H, C.sub.1
-C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.1 -C.sub.4
alkylcarbonyl, C.sub.1 -C.sub.6 alkoxycarbonyl, or C.sub.1 -C.sub.6
haloalkoxycarbonyl; R.sub.12 and R.sub.13 are each independently H
or C.sub.1 -C.sub.6 alkyl; G is H; C.sub.1 -C.sub.6 alkyl
optionally substituted with one or more halogen, C.sub.1 -C.sub.4
alkoxy, C.sub.1 -C.sub.6 haloalkoxy, CN, NO.sub.2 S(O).sub.u
R.sub.14, COR.sub.15, CO.sub.2 R.sub.16, phenyl or C.sub.3 -C.sub.6
cycloalkyl groups; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6
haloalkoxy; CN; NO.sub.2 ; S(O).sub.u R.sub.17 ; COR.sub.18 ;
CO.sub.2 R.sub.19 ; phenyl optionally substituted with one or more
halogen, CN, C.sub.1 -C.sub.3 haloalkyl, or C.sub.1 -C.sub.3
haloalkoxy groups; C.sub.3 -C.sub.6 cycloalkyl; or phenylthio; Q is
phenyl optionally substituted with one or more halogen, CN, SCN,
NO.sub.2, S(O).sub.u R.sub.20, C.sub.1 -C.sub.4 alkyl, C.sub.1
-C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxyalkyl, C.sub.1 -C.sub.6
alkoxy, C.sub.1 -C.sub.6 haloalkoxy, or NR.sub.21 R.sub.22 groups;
u is an integer of 0, 1 or 2; R.sub.14, R.sub.15, R.sub.16,
R.sub.18, R.sub.19, R.sub.21 and R.sub.22 are each independently H
or C.sub.1 -C.sub.6 alkyl; R.sub.17 and R.sub.20 are each
independently C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 haloalkyl;
R.sub.33 is CO.sub.2 R.sub.34 ; R.sub.34 is H, C.sub.1 -C.sub.6
alkyl, C.sub.1 -C.sub.6 haloalkyl, phenyl or halophenyl; and the
dotted line configuration {character pullout} represents a double
bond or a single bond (i.e. C--N or C.dbd.N); or
a stereoisomer thereof.
Preferred neuronal sodium channel antagonists suitable for use in
the composition of the invention are those compounds of formula I,
II or III wherein the dotted line configuration {character pullout}
represents a double bond.
More preferred neuronal sodium channel antagonists suitable for use
in the inventive composition are those compounds of formula I or
formula III wherein the dotted line configuration represents a
double bond.
Particularly preferred neuronal sodium channel antagonists useful
in the composition of the invention are those compounds of formula
I or formula III wherein W is O; X is trifluoromethoxy and is in
the 4-position; Y is trifluoromethyl and is in the 3-position; Z is
CN and is in the 4-position; A is CH.sub.2 ; n is 0; m, p and q are
each 1; R and R.sub.1 are each H; Z' is Cl; R.sub.33 and G are each
CO.sub.2 CH.sub.3 ; Q is p-(trifluoromethoxy)phenyl; and the dotted
line configuration {character pullout} represents a double bond; or
a stereoisomer thereof.
Further neuronal sodium channel antagonist compounds include those
described in U.S. Pat. Nos. 5,116,850 and 5,304,573, among other
publications. Exemplary of further neuronal sodium channel
antagonist compounds suitable for use in the composition of the
invention are those compounds having structural formula
##STR3##
wherein W is O or S; X" and Y" are each independently H; halogen;
CN; SCN; C.sub.1 -C.sub.6 alkyl optionally substituted with one or
more halogen, NO.sub.2, CN, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 alkylthio, phenyl, halophenyl, C.sub.1 -C.sub.4
alkylsulfonyl, C.sub.1 -C.sub.4 haloalkylsulfonyl, or C.sub.1
-C.sub.4 alkoxycarbonyl groups; C.sub.2 -C.sub.4 alkenyl; C.sub.2
-C.sub.4 haloalkenyl; C.sub.2 -C.sub.4 alkynyl; C.sub.2 -C.sub.4
haloalkynyl; C.sub.3 -C.sub.6 cycloalkyl; C.sub.3 -C.sub.6
halocycloalkyl; phenyl optionally substituted with one or more
halogen, CN, NO.sub.2, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4
haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy,
C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfonyl or
C.sub.1 -C.sub.4 haloalkylsulfonyl groups; C.sub.1 -C.sub.4
alkylcarbonyl; C.sub.1 -C.sub.4 haloalkylcarbonyl; or NR.sub.28
R.sub.29 ; m is an integer of 1, 2, 3, 4, or 5; G' is phenyl
optionally substituted with one or more groups which may be the
same or different selected from X"; a 5-membered heteroaromatic
ring containing one or two heteroatoms selected from 0 or 1 oxygen,
0 or 1 sulfur and 0, 1 or 2 nitrogen atoms said 5-membered
heteroaromatic ring being attached via carbon and being optionally
substituted with one or more groups which may be the same or
different selected from X"; or a 6-membered heteroaromatic ring
containing one or two heteroatoms selected from 0 or 1 oxygen, 0 or
1 sulfur and 0, 1 or 2 nitrogen atoms said 6-membered
heteroaromatic ring being attached via carbon and being optionally
substituted with one or more groups which may be the same or
different selected from X"; Q' is H; C.sub.1 -C.sub.6 alkyl
optionally substituted with one or more halogen, CN, C.sub.1
-C.sub.3 alkoxy, C.sub.1 -C.sub.6 alkoxycarbonyl, or phenyl
optionally substituted with one or more halogen, CN, NO.sub.2,
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1
-C.sub.4 alkylsulfonyl or C.sub.1 -C.sub.4 alkylsulfinyl groups;
C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 alkynyl; or phenyl
optionally substituted with one to three groups, which may be the
same or different, selected from X"; R.sub.23, R.sub.24, R.sub.25,
R.sub.26, R.sub.27, R.sub.28 and R.sub.29 are each independently H
or C.sub.1 -C.sub.4 alkyl; and the dotted line configuration
{character pullout} represents a double bond or a single bond (i.e.
C--N or C.dbd.N); or
a stereoisomer thereof.
Further preferred neuronal sodium channel antagonist compounds of
the invention are those compounds of formula IV or V wherein the
dotted line configuration {character pullout} represents a double
bond.
Other preferred neuronal sodium channel antagonist compounds
suitable for use in the composition of the invention are those
compounds of formula IV or V wherein W is O; X" and Y" are each
independently H or C.sub.1 -C.sub.6 haloalkyl; m is 1; R.sub.23,
R.sub.24, R.sub.25, R.sub.26 and R.sub.27 are each H; G is phenyl
optionally substituted with one or more halogen atoms; Q' is
halophenyl or C.sub.1 -C.sub.4 alkyl optionally substituted with
one phenyl or halophenyl group; and the dotted line configuration
{character pullout} represents a double bond; or a stereoisomer
thereof.
Arylpyrrole insecticides include those described in U.S. Pat. Nos.
5,010,098; 5,492,925; 5,484,807 and 5,284,863, among other
publications. Exemplary of the arylpyrrole insecticides suitable
for use in the composition of the invention are those arylpyrroles
having the structural formula ##STR4## Hal is Cl or Br; x is an
integer of 1, 2, 3, 4, 5 or 6; D is H; C.sub.1 -C.sub.6 alkyl
optionally substituted with one or more halogen, CN, OH, C.sub.1
-C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.5
alkylthio, C.sub.1 -C.sub.4 alkylcarbonyloxy, C.sub.1 -C.sub.4
haloalkylthio, C.sub.1 -C.sub.6 alkenylcarbonyloxy,
phenylcarbonyloxy, halophenylcarbonyloxy, phenoxy, halophenoxy,
phenyl, halophenyl or C.sub.1 -C.sub.3 alkylphenyl groups, C.sub.2
-C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; CN; C.sub.2
-C.sub.6 alkynyl; C.sub.2 -C.sub.6 haloalkynyl; di-(C.sub.1
-C.sub.4 alkyl)aminocarbonyl; or C.sub.3 -C.sub.6
polymethyleneiminocarbonyl; L is H or halogen; M and M' are each
independently H, halogen, CN, NO.sub.2, C.sub.1 -C.sub.4 alkyl,
C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1
-C.sub.4 haloalkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4
haloalkylthio, C.sub.1 -C.sub.4 alkylsufonyl, C.sub.1 -C.sub.4
haloalkylsulfonyl, C.sub.1 -C.sub.4 alkylcarbonyl, C.sub.1 -C.sub.4
haloalkylcarbonyl, NR.sub.35 R.sub.36 or when M and M.sup.1 are
attached to adjacent carbon atoms, they may be taken together with
the carbon atoms to which they are attached to form a ring in which
MM.sup.1 represents --OCH.sub.2 O--, --OCF.sub.2 O-- or
--CH.dbd.CH--CH.dbd.CH--; A' is O or S; R.sub.30, R.sub.31 and
R.sub.32 are each independently hydrogen, halogen, NO.sub.2, CHO or
R.sub.31 and R.sub.32 may be taken together with the carbon atoms
to which they are attached to form a ring in which R.sub.31
R.sub.32 represent ##STR5## L', L", T and V are each independently
H, halogen, CN or NO.sub.2 with the proviso that no more than two
of L', L", T or V are NO.sub.2 ; and R.sub.35 and R.sub.36 are each
independently H or C.sub.1 -C.sub.4 alkyl.
Preferred arylpyrroles suitable for use as one essential active
ingredient in the composition of the invention are those
arylpyrroles of formula VI wherein D is H or ethoxymethyl; Ar is
phenyl substituted with one or more halogen or halomethyl groups;
and n is 1.
Preferred embodiments of the invention are those having a neuronal
sodium channel antagonist compound of formula I or formula III and
an arylpyrrole compound of formula VI as active ingredients.
More preferred embodiments of the invention are those having a
formula I or formula III compound wherein W is O; X is
trifluoromethoxy and is in the 4-position; Y is trifluoromethyl and
is in the 3-position; Z is CN and is in the 4-position; A is
CH.sub.3 ; n is 0; m, p and q are each independently 1; R and
R.sub.1 are each independently H; Z is Cl;, R.sub.33 and G are each
independently CO.sub.2 CH.sub.3 ; Q is p-(trifluoromethoxy)phenyl;
and the dotted line configuration {character pullout} represents a
double bond and a formula VI arylpyrrole wherein D is H or
ethoxymethyl; Ar is phenyl substituted with one or more halogen or
halomethyl groups; and x is 1.
Particularly preferred embodiments of the invention are those
having as the active ingredients a compound of formula I or III
wherein W is O; X is trifluoromethoxy and is in the 4-position; Y
is trifluoromethyl and is in the 3-position; Z is CN and is in the
4-position; A is CH.sub.3 ; n is 0; m, p and q are each 1; R and
R.sub.1 are each H; Z' is Cl;, R.sub.33 and G are each CO.sub.2
CH.sub.3 ; and Q is p-(trifluoromethoxy)phenyl, and the dotted line
configuration {character pullout} represents a double bond and an
arylpyrrole of formula VI wherein D is H or ethoxymethyl; Ar is
p-chlorophenyl or 3,5-dichlorophenyl; and x is 1.
In the specification and claims the term haloalkyl designates an
alkyl group C.sub.x H.sub.2x+1 having 1 to 2x+1 halogen atoms which
may be the same or different. Similarly, the terms haloalkenyl,
haloalkynyl, haloalkoxy, halophenyl and the like designate mono- to
perhalogen substitution wherein the halogens may be the same or
different. Halogen designates Cl, Br, I or F.
Each of the compounds of formula I, II, III, IV and V embody
assymetric centers which may be represented in the stereoisomeric
R-form or S-form. The present invention also includes the R-form,
the S-form or mixtures comprising the R-form and the S-form in any
ratio. For compounds of formula III, the S-form is preferred.
Advantageously, the neuronal sodium-channel antagonist compound of
formula I, II, III, IV or V or a mixture thereof may be formulated
with an arylpyrrole insecticide. Said formulation may then be
dispersed in a solid or liquid diluent for application to the
insect, its food supply, breeding ground or habitat as a dilute
spray or as a solid dust or dust concentrate. Customary formulation
adjuvants as well as additional agriculturally acceptable active
ingredients may be added and are within the scope of the
invention.
The active ingredients of the inventive composition may also be
formulated separately as a wettable powder, emulsifiable
concentrate, aqueous or liquid flowable, suspension concentrate or
any one of the conventional formulations used for insect control
agents and tank mixed in the field with water or other inexpensive
liquid for application as a liquid spray mixture. The separately
formulated compositions may also be applied sequentially.
In actual practice, the composition of the invention is applied to
the plant foliage or plant stem or insect habitat as a dilute spray
prepared from any of the above-said formulations. In practice it
has been found that the active ingredients of the composition of
the invention are highly synergistic when present at a ratio of
neuronal sodium channel antagonist compound to arylpyrrole
insecticide of about 1:10 to 1:50.
The compositions of the invention are superior insecticidal
compositions and are especially useful for protecting growing and
harvested plants including: leguminous crops such as soybeans, snap
beans, peas, wax beans and the like as well as cotton, forage
crops, cole crops, leafy vegetables, tobacco, hops, tomatoes,
potatoes, flowering ornamentals such as chrysanthemums, vine crops
such as grapes, squash, pumpkin or melon and fruit trees such as
cherry, peach, apple or citrus, from the ravages of insects.
The synergistic insecticidal composition of the invention is found
to be highly active against a wide variety of lepidopteran and
coleopteran insects such as Helicoverpa zea (cotton bollworm),
Heliothis virescens (tobacco budworm), Leptinotarsa decemlineata
(Colorado potato beetle), Diabrotica spp. (corn rootworm) and the
like.
Further, the composition of the invention may be useful in the
prevention and control of public health pests such as houseflies,
mosquitoes, cockroaches, ants, termites or the like.
These and other advantages of the invention may become more
apparent from the examples set forth herein below. These examples
are provided merely as illustrations of the invention and are not
intended to be construed as a limitation thereof.
EXAMPLE 1
Evaluation of the Synergistic Insecticidal Effect of a Combination
of a Neuronal Sodium Channel Antagonist Plus an Arylpyrrole
Insecticide
In this evaluation, the Heliothis zea (cotton bollworm), Heliothis
virescens (tobacco budworm) and pyrethroid-resistant Heliothis
virescens larvae used are obtained from laboratory colonies.
Pyrethroid-resistant H. virescens are derived from the PEG-strain
[Campannola & Plapp, Proceedings of Beltwide Cotton Conference
(1988)].
Cotton leaves are immersed in 1:1 v/v, acetone/water solutions of
test compound, or solutions of a combination of test compounds for
a period of about 3 seconds. Following immersion, leaves are
allowed to air-dry for 2-3 hours. Plastic bioassay trays containing
multiple open-faced wells (4.0.times.4.0.times.2.5 cm) are used as
the test arenas. Cut portions of a treated leaf, a moistened cotton
dental wick and a single third-instar larva are placed into each
well, covered with an adhesive vented clear plastic sheet and held
under constant fluorescent light at about 27.degree. C. for a
predetermined period of time. Larval mortality/morbidity is
evaluated at 5 days after treatment. All treatments are replicated
4-5 fold in a randomized complete block design with 16-32 larvae
per treatment. A log-probit analysis is applied to all data
obtained. The results are summarized in Tables I, II and III
hereinbelow.
TABLE I Evaluation of the Synergistic Control of Cotton Bollworm %
Larval Toxicity Treatment Dose (ppm) Mortaliity Ratio.sup.3,4
A.sup.1 0.816 0 -- B.sup.2 0.0816 9 -- A + B 0.816 + 0.0816 50 5.6
A 1.0 9.4 -- B 0.1 19.8 -- A + B 1.0 + 0.1 62.5 2.1 .sup.1 A =
formula VIa arylpyrrole .sup.2 B = formula Ia neuronal sodium
channel antagonist ##EQU1## .sup.4 Toxicity Ratio > 1 =
synergistic
##STR6##
TABLE II Evaluation of the Synergistic Control of Tobacco Budworm %
Larval Toxicity Treatment Dose (ppm) Mortaliity Ratio.sup.3,4
A.sup.1 0.974 3 -- B.sup.2 0.0974 25 -- A + B 0.974 + 0.0974 50 1.8
A 1.0 10 -- B 0.1 30 -- A + B 1.0 + 0.1 51.3 1.28 .sup.1 A =
formula VIa arylpyrrole .sup.2 B = formula Ia neuronal sodium
channel antagonist ##EQU2## .sup.4 Toxicity Ratio > 1 =
synergistic
##STR7##
TABLE III Evaluation of the Synergistic Control of Pyrethroid-
Resistant Tobacco Budworm % Larval Toxicity Treatment Dose (ppm)
Mortaliity Ratio.sup.3,4 A.sup.1 0.997 0 -- B.sup.2 0.0997 29 -- A
+ B 0.997 + 0.0997 50 1.7 A 2.093 7 -- B 0.0419 8 -- A + B 2.093 +
0.0419 50 3.3 A 1.0 6.2 -- B 0.1 25.0 -- A + B 1.0 + 0.1 56.3 1.8 A
3.0 34.4 -- B 0.06 14.1 -- A + B 3.0 + 0.06 81.2 1.67 .sup.1 A =
formula VIa arylpyrrole .sup.2 B = formula Ia neuronal sodium
channel antagonist ##EQU3## .sup.4 Toxicity Ratio > 1 =
synergistic
##STR8##
* * * * *